Methods of making triamine solids

ABSTRACT

Methods of making triamine solids are disclosed. Solids including free-flowing powders, to pressed, cast, extruded or other solids are disclosed. Compositions employing the solid triamines are provided and methods of use thereof are particularly suitable for cleaning, disinfecting, sanitizing, rinsing and/or lubricating are disclosed.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority and is related to U.S. ProvisionalApplication Ser. No. 62/219,760 filed on Sep. 17, 2015. The entirecontents of this patent application are hereby expressly incorporatedherein by reference including, without limitation, the specification,claims, and abstract, as well as any figures, tables, or drawingsthereof.

FIELD OF THE INVENTION

The invention relates to methods of making triamine solids, includingstable, free-flowing powders and other solid forms of triamine rawmaterials. Compositions employing the solid triamines and methods of useare provided. Beneficially, the triamine solids provide antimicrobial,sanitizing and disinfectant properties for use in various compositionformulations and applications of use. Methods of use for variouscleaning, disinfecting, sanitizing, rinsing and/or lubricating aredisclosed.

BACKGROUND OF THE INVENTION

There is an ongoing need for effective cleaning products as multiplesoils are present in institutional and other settings requiring theremoval of, cleaning, sanitizing and/or disinfecting of protein, fat andoil, and starch-based soils. Such soils can be difficult to remove fromhard surfaces and soft surfaces, requiring aggressive cleaning products.Liquid triamine antimicrobial compositions may provide cleaning,disinfecting, sanitizing, rinsing and/or lubricating benefits. However,the amine providing antimicrobial activity(N,N-Bis(3-aminopropyl)dodecylamine) in its unaltered state is difficultto formulate into solid compositions. The liquid form of the aminesconventionally requires use of diluted liquid compositions and presentsnumerous barriers to solid formulation of the triamine antimicrobialcompositions. Further, the formulation of solid triamine composition hasrequired the addition of numerous functional ingredients which dilutethe concentration of triamine in solid antimicrobial conditions, thusimparing the efficacy of the composition

Accordingly, it is an objective of the claimed invention to developmethods for making solid triamine as a raw material. As such, it is afurther objective of the claimed invention to develop methods ofsolidification of a composition consisting essentially of triamine andan acid.

According to an objective of the claimed invention, such raw materialsare suitable for various applications of use, including for example,formulation into various antimicrobial, sanitizing and disinfectantcompositions for cleaning, disinfecting, sanitizing, rinsing,lubricating and/or other applications.

In an aspect of the invention, methods of making solid triamines providea valuable raw material, including solid forms ranging from freeflowable powders to pressed solids.

Other objects, advantages and features of the present invention willbecome apparent from the following specification taken in conjunctionwith the accompanying drawings.

BRIEF SUMMARY OF THE INVENTION

In an embodiment, the present invention provides methods of making solidtriamine compositions, compositions employing the solid triamines, andmethods of using the same.

In an embodiment, a method of making a solid triamine compositioncomprises mixing a triamine and an acid, wherein the ratio of the acidto the triamine is from about 1:10 to about 1:1; and at least partiallyneutralizing the triamine to a pH of about 6-11 to form a solid aminesalt. In an aspect, the acid is a monoacid or diacid. In an aspect, thetriamine has any one of the following formulas:

R—NH—(CH₂)_(r)NH₂   (1a)

R—NH—(CH₂)_(r)N⁺H₃X″  (1b)

R—N⁺H₂—(CH₂)_(r)NH₃2X⁻  (1c)

R—NH——[(CH₂)_(r)NH]_(y)—(CH₂)_(m)—NH₂   (2a)

R—NH—[(CH₂)_(r)—NH]_(y)(CH₂)_(m)—NH₂(H⁺X⁻)_(n)   (2b)

R₂—NY   (3a)

R₂—NY2⁺X″  (3b)

Wherein: R is a linear or branched alkyl residue with 6 to 22C atoms; Yindependently represents hydrogen or a methyl group; X″ is an equivalentof an anion comprising an amidosulfonate, nitrate, halide, sulfate,hydrogen carbonate, carbonate, phosphate, hydroxide, carboxylate, and/ororganic acid; m, r, and y independently represent an integer rangingfrom 1 to 6; and n is an integer ranging from 1 to 2+y.

In an embodiment of the invention, a method of cleaning, sanitizingand/or disinfecting comprises generating a solid triamine and optionallyadding additional functional ingredients to the solid triamine and/orforming a composition comprising the solid triamine and additionalfunctional ingredients, and contacting an article or surface with a usesolution of the solid triamine and/or a use solution of the compositionfor cleaning, sanitizing, and/or disinfecting. In an aspect, thecleaning, sanitizing, and/or disinfecting is a rinse step and/orlubricating step. In an aspect, the use solution of the solid triamineand/or compositions comprising the solid triamines provides betweenabout 1 ppm to about 1000 ppm triamine, and between about 1 ppm to about500 ppm acid.

While multiple embodiments are disclosed, still other embodiments of thepresent invention will become apparent to those skilled in the art fromthe following detailed description, which shows and describesillustrative embodiments of the invention. Accordingly, the drawings anddetailed description are to be regarded as illustrative in nature andnot restrictive.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

The present invention relates to solid triamine antimicrobial,sanitizing, disinfecting, cleaning, rinsing and/or lubricatingcompositions. The compositions have advantages over conventional liquidtriamine compositions, including for example, minimized costs fortransportation and shipment, generation of use solutions at a point ofuse, and the like.

The embodiments of this invention are not limited to particular methodsof making solid triamine as a raw material source, compositionsemploying the solid triamines, and/or methods of using the same, whichcan vary and are understood by skilled artisans. It is further to beunderstood that all terminology used herein is for the purpose ofdescribing particular embodiments only, and is not intended to belimiting in any manner or scope. For example, as used in thisspecification and the appended claims, the singular forms “a,” “an” and“the” can include plural referents unless the content clearly indicatesotherwise. Further, all units, prefixes, and symbols may be denoted inits SI accepted form.

Numeric ranges recited within the specification are inclusive of thenumbers within the defined range. Throughout this disclosure, variousaspects of this invention are presented in a range format. It should beunderstood that the description in range format is merely forconvenience and brevity and should not be construed as an inflexiblelimitation on the scope of the invention. Accordingly, the descriptionof a range should be considered to have specifically disclosed all thepossible sub-ranges as well as individual numerical values within thatrange (e.g. 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, and 5).

So that the present invention may be more readily understood, certainterms are first defined. Unless defined otherwise, all technical andscientific terms used herein have the same meaning as commonlyunderstood by one of ordinary skill in the art to which embodiments ofthe invention pertain. Many methods and materials similar, modified, orequivalent to those described herein can be used in the practice of theembodiments of the present invention without undue experimentation, thepreferred materials and methods are described herein. In describing andclaiming the embodiments of the present invention, the followingterminology will be used in accordance with the definitions set outbelow.

The term “about,” as used herein, refers to variation in the numericalquantity that can occur, for example, through typical measuring andliquid handling procedures used for making concentrates or use solutionsin the real world; through inadvertent error in these procedures;through differences in the manufacture, source, or purity of theingredients used to make the compositions or carry out the methods; andthe like. The term “about” also encompasses amounts that differ due todifferent equilibrium conditions for a composition resulting from aparticular initial mixture. Whether or not modified by the term “about”,the claims include equivalents to the quantities.

The term “actives” or “percent actives” or “percent by weight actives”or “actives concentration” are used interchangeably herein and refers tothe concentration of those ingredients involved in cleaning expressed asa percentage minus inert ingredients such as water or salts.

As used herein, the term “cleaning” refers to a method used tofacilitate or aid in soil removal, bleaching, microbial populationreduction, and any combination thereof. As used herein, the term“microorganism” refers to any noncellular or unicellular (includingcolonial) organism. Microorganisms include all prokaryotes.Microorganisms include bacteria (including cyanobacteria), spores,lichens, fungi, protozoa, virinos, viroids, viruses, phages, and somealgae. As used herein, the term “microbe” is synonymous withmicroorganism.

As used herein, the term “disinfectant” refers to an agent that killsall vegetative cells including most recognized pathogenicmicroorganisms, using the procedure described in A.O.A.C. Use DilutionMethods, Official Methods of Analysis of the Association of OfficialAnalytical Chemists, paragraph 955.14 and applicable sections, 15thEdition, 1990 (EPA Guideline 91-2). As used herein, the term “high leveldisinfection” or “high level disinfectant” refers to a compound orcomposition that kills substantially all organisms, except high levelsof bacterial spores, and is effected with a chemical germicide clearedfor marketing as a sterilant by the Food and Drug Administration. Asused herein, the term “intermediate-level disinfection” or “intermediatelevel disinfectant” refers to a compound or composition that killsmycobacteria, most viruses, and bacteria with a chemical germicideregistered as a tuberculocide by the Environmental Protection Agency(EPA). As used herein, the term “low-level disinfection” or “low leveldisinfectant” refers to a compound or composition that kills someviruses and bacteria with a chemical germicide registered as a hospitaldisinfectant by the EPA.

The term “hard surface” refers to a solid, substantially non-flexiblesurface such as a counter top, tile, floor, wall, panel, window,plumbing fixture, kitchen and bathroom furniture, appliance, engine,circuit board, and dish. Hard surfaces may include for example, healthcare surfaces and food processing surfaces, and further includeinstruments.

As used herein, the term “sanitizer” refers to an agent that reduces thenumber of bacterial contaminants to safe levels as judged by publichealth requirements. In an embodiment, sanitizers for use in thisinvention will provide at least a 3 log reduction and more preferably a5-log order reduction. These reductions can be evaluated using aprocedure set out in Germicidal and Detergent Sanitizing Action ofDisinfectants, Official Methods of Analysis of the Association ofOfficial Analytical Chemists, paragraph 960.09 and applicable sections,15th Edition, 1990 (EPA Guideline 91-2). According to this reference asanitizer should provide a 99.999% reduction (5-log order reduction)within 30 seconds at room temperature, 25±2° C., against several testorganisms.

As used herein, the term “soil” or “stain” refers to a non-polar oilysubstance which may or may not contain particulate matter such asmineral clays, sand, natural mineral matter, carbon black, graphite,kaolin, environmental dust, etc.

Differentiation of antimicrobial “-cidal” or “-static” activity, thedefinitions which describe the degree of efficacy, and the officiallaboratory protocols for measuring this efficacy are considerations forunderstanding the relevance of antimicrobial agents and compositions.Antimicrobial compositions can affect two kinds of microbial celldamage. The first is a lethal, irreversible action resulting in completemicrobial cell destruction or incapacitation. The second type of celldamage is reversible, such that if the organism is rendered free of theagent, it can again multiply. The former is termed microbiocidal and thelater, microbistatic. A sanitizer and a disinfectant are, by definition,agents which provide antimicrobial or microbiocidal activity. Incontrast, a preservative is generally described as an inhibitor ormicrobistatic composition

For the purpose of this patent application, successful microbialreduction is achieved when the microbial populations are reduced by atleast about 50%, or by significantly more than is achieved by a washwith water. Larger reductions in microbial population provide greaterlevels of protection.

As used herein, the term “substantially free” refers to compositionscompletely lacking the component or having such a small amount of thecomponent that the component does not affect the performance of thecomposition. The component may be present as an impurity or as acontaminant and shall be less than 0.5 wt-%. In another embodiment, theamount of the component is less than 0.1 wt-% and in yet anotherembodiment, the amount of component is less than 0.01 wt-%.

The term “weight percent,” “wt-%,” “percent by weight,” “% by weight,”and variations thereof, as used herein, refer to the concentration of asubstance as the weight of that substance divided by the total weight ofthe composition and multiplied by 100. It is understood that, as usedhere, “percent,” “%,” and the like are intended to be synonymous with“weight percent,” “wt-%,” etc.

The methods and compositions of the present invention may comprise,consist essentially of, or consist of the components and ingredients ofthe present invention as well as other ingredients described herein. Asused herein, “consisting essentially of” means that the methods andcompositions may include additional steps, components or ingredients,but only if the additional steps, components or ingredients do notmaterially alter the basic and novel characteristics of the claimedmethods and compositions.

Solid Triamines

The solid triamines of the present invention are provided in any stablesolid form. A “stable solid” composition refers to a solid that retainsits shape under conditions in which the composition may be stored orhandled. As referred to herein a “solid” triamine is that which remainsat temperatures up to about up to about 100° F. (45° C.), or preferablyup to about 122° F. (50° C.).

The solid triamines according to the invention can take various forms,shapes and densities. In an aspect, stable solid triamines have varyingdegrees of hardness, ranging from that of a flowable or free-flowingpowder to a fused solid. In an aspect, the solid triamines includepowders, such as free-flowing powders. In some aspects, flowing powdersand solids may have a consistency similar to wet sand. In certainaspects, the solid triamines can be a powder or a wetted powder, such asthose which are relatively dense and have a consistency characterized asbeing a hardened paste. In an aspect, stable solid triamines includefriable solids. In further aspects, the stable solid triamines includemolded, pressed, block and/or extruded solids. In further aspects, thestable solid triamines are cured solids.

Beneficially, the solid triamines produced according to the methods ofthe invention are suitable for use in varying applications. The solidtriamines can further be formulated into various solid compositionscontaining the solid triamines, including for example, any pressed,extruded, block and/or cast solid compositions. Still further, accordingto the invention the solid triamines can be formulated into variouscompositions to be utilized for any molded or formed solid pellet,block, tablet, powder, granule, flake or the formed solid can thereafterbe ground or formed into a powder, granule, or flake.

Exemplary ranges of the solid triamines according to the invention areshown in Tables 1A-1B in weight percentage of the solid compositions.

TABLE 1A First Second Third Fourth Exemplary Exemplary ExemplaryExemplary Material Range wt-% Range wt-% Range wt-% Range wt-% Triamine10-99  20-90 10-50 50-90 Acid  1-50 2.5-40  2-40  5-40

TABLE 1B First Second Third Fourth Exemplary Exemplary ExemplaryExemplary Material Range wt-% Range wt-% Range wt-% Range wt-% Triamine10-99  20-90 20-50 20-40 Acid 1-50 2.5-40   5-40  5-20 Additional 0-50 0-50 30-75 30-50 Functional Ingredients

In an aspect the ratio of the acid to triamine in the solid triaminesand methods of making the same is from about 1:10 to about 1:1, fromabout 1:10 to about 1:5, from about 1:5 to about 1:3, or from about 1:3to about 1:1. In a further aspect, the ratio of the acid to the triaminecan be any combination below the 1:10 ratio, including for example 1:1,1:0.5, etc. According to the invention the biocidal triamine is thedominant species in the solid compositions. In a preferred aspect, theratio of acid to triamine is from about 1:3 to about 1:2.

According to embodiments of the invention, the solid triamine ispartially neutralized. In an aspect, the solid triamine has a pH fromabout 6-11, from about 6.5-9.5, and preferably from about 7-9 or about8.

Biocidal Triamine

The solid triamines according to the invention include at least onebiocidal triamine combined according to the methods of making of theinvention. As referred to herein the biocidal triamine may be referredto as a bis (3-aminopropyl) dodecylamine, 1,3-propanediamine,N-(3-aminopropyl)-N-dodecylamine, Dodecylamine, orN,N-bis(3-aminopropyl) laurylamine, or may be represented by the formula

wherein R is a linear or branched alkyl residue with C1-22,C1-C18, orC1-12. The residue R of the amines can be saturated, unsaturated, mono-or polyunsaturated. In a preferred aspect R is a straight chain alkylgroup, preferably C1-C12, or more preferably C₁₂H₂₅. Such amines can beproduced according to processes known in the literature and/or areavailable as commercial products. A commercially available biocidaltriamine is available under the tradename Lonzabac® sold by Lonza Inc.Further commercially available biocidal triamines includeN-coco-1,3-propylene diamine, N-oleyl-1,3-propylene diamine,N-tallow-1,3-propylene diamine, mixtures thereof, or salts thereof, suchN-alkyl-1,3-propylene diamines are available from Akzo Chemie Americaand Armak Chemicals.

As referred to herein the biocidal triamine may further be described asan alkylamine. The biocidal triamine may further be described as analkylamine of mono-, di- and/or polyamines. Exemplary biocidal triaminemay include, for example, those selected from the following formulas:

R—NH—(CH₂)_(r)NH₂   (1a)

R—NH—(CH₂)_(r)N⁺H₃X″  (1b)

R—N⁺H₂—(CH₂)_(r)NH₃2X⁻  (1c)

R—NH——[(CH₂)_(r)NH]_(y)—(CH₂)_(m)—NH₂   (2a)

R—NH—[(CH₂)_(r)—NH]_(y)(CH₂)_(m)—NH₂(H⁺X⁻)_(n)   (2b)

R₂—NY   (3a)

R₂—NY2⁺X″  (3b)

wherein, R is a linear or branched alkyl residue, preferably with 6 to22C atoms, wherein Y independently represents hydrogen or a methylgroup, wherein X″ is an equivalent of an anion, selected from the groupcomprising an amidosulfonate, nitrate, halide, sulfate, hydrogencarbonate, carbonate, phosphate, hydroxide, carboxylate, and/or organicacid, wherein m, r, and y independently represent an integer rangingfrom 1 to 6, and wherein n is an integer ranging from 1 to 2+y.

In an aspect, the residue R of the amines can be a linear or branchedalkyl residue with 6C atoms to 22C atoms, preferably 8C atoms to 20Catoms, further preferred 10C atoms to 18C atoms and also preferred 12Catoms to 16C atoms or 14C atoms. In a further aspect, the residue R ofthe amines can be saturated, unsaturated, mono- or polyunsaturated. In astill further aspect, preferred amines include amines, wherein R is C8to C18 alkyl, most preferred C8 to C12 alkyl. In an aspect, m, r, and yindependently represent an integer ranging from 2 to 5 or 3 to 4 andmost preferred 3.

In an aspect, dialkylamines, trialkylamines, alkyldiamines and/oralkyltriamines can be preferred, selected from the group comprisingcocopropylenediamine, oleyldipropylenetriamine,tallowdipropylenetriamine, oleylpropylenediamine,tallow-dipropylenetriamine, oleyltripropylenetetramine,N-3-aminopropyl-N-dodecyl-1,3-propane-diamine and/or a salt with X″thereof. The anion X″ can be selected from the group comprising anamidosulfonate, nitrate, halide, sulfate, hydrogen carbonate, carbonate,phosphate, hydroxide, carboxylate, and/or organic acid.

As referred to herein the biocidal triamine may further be described asan alkanolamine. Exemplary biocidal triamine may include, for example,those selected from the following formulas:

where m and, if present, o and p independently of one another have thevalue 2 or 3, and x and y independently of one another have the value 0or 1, or a corresponding salt; in the mass ratio (I):(II) of 20:1 to1:20. Alkyl, here and hereinafter, is taken to mean in each caseunbranched or branched alkyl groups of the specified number of carbons,and particularly preferably those having an even number of carbon atoms.

Exemplary alkanolamines are in principle all ethanolamines andpropanolamines, in particular mono-ethanolamine, diethanolamine,triethanolamine and 3-amino-1-propanol. In an aspect, a preferredalkanolamine compound has a primary amino group, that is to say usingmonoethanolamine and 3-amino-1-propanol.

In an aspect, the biocidal amines for use according to the invention mayinclude any mixture of different amines, or alkylamines, oralkanolamines.

As referred to herein, the biocidal amines may correspond to any of thegeneral formulas, and can be produced according to processes known inthe literature and/or are available as commercial products.

In an aspect, the biocidal triamine concentration may be dependent uponthe desired pH of the use solution generated from the solid formulation.It is an unexpected benefit of the present invention that the triaminecompositions with high active concentrations of the biocidal triaminesare solids.

In an aspect, the solid triamines include from about 10 wt-% to about 99wt-% biocidal triamine, from about 20 wt-% to about 90 wt-% biocidaltriamine, or from about 50 wt-% to about 90 wt-% biocidal triamine. Inother aspects including those where additional functional ingredientsare included in the formulations, the solid triamines include from about5 wt-% to about 75 wt-% biocidal triamine, from about 5 wt-% to about 50wt-% biocidal triamine, or from about 10 wt-% to about 25 wt-% biocidaltriamine. Without being limited according to the invention, all rangesrecited are inclusive of the numbers defining the range and include eachinteger within the defined range.

Acids

The solid triamine according to the invention include at least one acidcombined according to the methods of making of the invention. The acidmay be organic or inorganic. The acid is preferably an organic acid. Inan aspect the acid may be an organic monocarboxylic acid or an organicdicarboxylic acid. In an aspect, the acid is a solid acid, preferably adiacid. In one aspect of the invention, the solid triamine compositioncomprises a monoacid having the following structure: R—COOH wherein R isa C4-C20 branched or linear alkyl group, preferably an alkane or alkene.

In an aspect, the solid triamine composition comprises a diacid havingthe structure (a) as shown:

wherein n=1-20, R₁ is H, C1-C8 alkyl or COOH; R₂ is H, C1-C8 alkyl, NH₂,OH, or COOH, and R₁ and R₂ substitution occurs on at least one carbonwithin C1-C20 chain.

In an aspect, the solid triamine composition comprises a diacid havingthe structure (b) as shown:

wherein: R₁ and R₂ are each COOH; R₃, R₄, R₅ and R₆ independently are H,C1-C8 alkyl, OH, or NH₂; R₁ and R₃ are each COOH; R₂, R₄, R5, and R₆independently are H, C1-C8 alkyl, OH, or NH₂; R₁ and R₄ are each COOH;R₂, R₃, R₅, and R₆ independently are H, C1-C8 alkyl, OH, or NH₂; R₁ andR₅ are each COOH; R₂, R₃, R₄, and R₆ independently are H, C1-C8 alkyl,OH, or NH₂; or R₁ and R₆ are each COOH; R₂, R₃, R₄, and R₅ independentlyare H, C1-C8 alkyl, OH, or NH₂.

In an aspect, the solid triamine composition comprises a diacid havingthe structure (c) as shown:

wherein: R₁ and R₂ are COOH; R₃, R₄, and R₅ independently are H, C1-C8alkyl, OH, or NH₂; R₁ and R₃ are COOH; R₂, R₄, R₅ independently are H,C1-C8 alkyl, OH, or NH₂; R₁ and R₄ are COOH; R₂, R₃, R₅ independentlyare H, C1-C8 alkyl, OH, or NH₂; or R₁ and R₅ are COOH; R₂, R₃, R₄independently are H, C1-C8 alkyl, OH, or NH₂.

In an aspect, the solid triamine composition comprises at least onediacid having the structures as shown and described as (a), (b), (c) orcombinations thereof.

Particularly preferred acids include citric acid, tartaric, malic,maleic, malonic, succinic, adipic, aspartic, glutamic, dipicolinic, anddodecanoic acid. Particularly preferred acids include the following:

Citric acid, 3-carboxy-3-hydroxypentanedioic acid,2-hydroxy-1,2,3-propanetricarboxylic acid, having the formula:

Tartaric acid, 2,3-dihydroxybutanedioic acid, 2,3-dihydroxysuccinicacid, threaric acid, racemic acid, uvic acid, paratartaric acid, havingthe formula:

Malic acid, 2-hydroxybutanedioic acid, having the formula:

Maleic acid, (Z)-butenedioic acid, cis-butenedioic acid, malenic acid,maleinic acid, toxilic acid, having the formula:

Glutamic acid, 2-aminopentanedioic acid, 2-aminoglutaric acid, havingthe formula:

Dipicolinic acid, pyridine-2,6-dicarboxylic acid,2,6-pyridinedicarboxylic acid, having the formula:

Succinic acid, Butanedioic acid, ethane-1,2-dicarboxylic acid, havingthe formula:

Adipic acid, hexanedioic acid, hexane-1,6-dicarboxylic acid,hexane-1,6-dioic acid, having the formula:

Dodecanedioic acid —C₁₂H₂₂O₄, having the formula:

Additional exemplary acids may include those organic acids selected fromthe group consisting of acetic acid, formic acid, propionic acid, citricacid, i.e., 2-hydroxy-1,2,3-propanetricarboxylic acid, lactic acid,tartaric acid, glycolic acid, salicylic acid, fumaric acid, malic acid,itaconic acid, ascorbic acid, succinic acid and benzoic acid.

Without being limited according to a mechanism of action, the acidpreferably provides a water-soluble salt of the triamine. In a preferredaspect, the acid generates a water-soluble salt of the triamine in asolid formulation.

In an aspect, the solid triamines include from about 1 wt-% to about 50wt-% acid, from about 5 wt-% to about 40 wt-% acid, or from about 10wt-% to about 35 wt-% acid. In other aspects, including those whereadditional functional ingredients are included in the formulations, thesolid triamines include from about 1 wt-% to about 35 wt-% acid, fromabout 1 wt-% to about 20 wt-% acid, or from about 2.5 wt-% to about 20wt-% acid. Without being limited according to the invention, all rangesrecited are inclusive of the numbers defining the range and include eachinteger within the defined range.

Water

The solid triamines according to the present invention can contain asmall amount of water. For example, components of the solid triaminesuch as the biocidal triamine may comprise water. Preferably water isnot added into the solid triamine and based on the total weight of thesolid composition there is a water content in the range of ≧0 wt-% to <5wt-%, preferably ≧0 wt-% to <2.5 wt-%, further preferred ≧0 wt-% to <1wt-%, furthermore preferred ≧0 wt-% to <0.5 wt-%. In some aspects,including those where additional functional ingredients are included inthe formulations, components with additional water content can beincluded in the composition, and preferably total water content of thesolid formulations is less than about 10 wt-%, less than about 9 wt-%,less than about 8 wt-%, less than about 7.5 wt-%, less than about 7wt-%, less than about 6 wt-%, or less than about 5 wt-%. Without beinglimited according to the invention, all ranges recited are inclusive ofthe numbers defining the range and include each integer within thedefined range.

Methods of Making Solid Triamines

Solid triamines suitable for use as a raw material for variouscomposition formulations are produced according to methods of theinvention. In an aspect, the solid triamines are generated by use of thebiocidal triamines and acids disclosed according to the invention. Suchcomponents suitable for use in the methods described herein for makingsolid triamines are defined above for the solid triamines of the presentinvention.

In an aspect, the triamine solids are made by a process comprisingmixing at least the biocidal triamine and the acid. In an aspect, thereaction of the biocidal triamine and the acid forms an amine salt. Asreferred to herein “mixing” can include any mechanisms (automated ormanual) as known to skilled artisans. In an aspect, a variety of mixerscan be employed to provide low shear mixing, including for exampleconical screw mixers including those with ribbons. In an aspect, aribbon blender or other apparatus providing high shear mixing is notemployed according to the invention.

The mixing step neutralizes the biocidal triamine to a pH from about 6to about 11. In an aspect, the triamine solids are made by mixing atleast the biocidal triamine and the acid to neutralize the biocidaltriamine to a pH from about 6.5 to about 9.5. In an aspect, the triaminesolids are made by mixing at least the biocidal triamine and the acid toneutralize the biocidal triamine to a pH from about 7 to about 9. Stillfurther, in an aspect, the triamine solids are made by mixing at leastthe biocidal triamine and the acid to neutralize the biocidal triamineto a pH of about 8. In an aspect, the alkaline pH of the biocidaltriamine is neutralized prior to the solidification.

In an aspect, the neutralization occurs during the mixing of thecomponents in a mixing vessel. The mixing vessels suitable for useaccording to the methods of the invention may vary in size, shape andmaterial, which will be determined based on a particular size of thebatch or continuous generation of the solid triamines according toembodiments of the invention.

In an aspect, mixing the components includes preferably mixing until ahomogeneous mixture is obtained. As one skilled in the art willascertain, the mixing of the components, including the biocidal triamineand the acid, may include various sequences of adding the components toobtain the mixture. The methods of generating the solid triamines arenot intended to be limited according to alterations in the process ofmanufacture involving the order of mixing the components describedherein.

The mixing of the biocidal triamine and acid to form the solid triaminemay be achieved using a batch or continuous mixing system. In anexemplary embodiment, a single- or twin-screw extruder is used tocombine and mix one or more components at high shear to form ahomogeneous mixture. In some embodiments, the processing temperature isat or below the melting temperature of the components. The processedmixture may be dispensed from the mixer by forming, casting or othersuitable means, whereupon the triamine hardens to a solid form. Thestructure of the matrix may be characterized according to its hardness,melting point, material distribution, crystal structure, and other likeproperties according to known methods in the art.

In an aspect, the solidification reaction occurs over a period fromabout 10 minutes to about 48 hours, or from about 15 minutes to about 24hours, or from about 30 minutes to about 12 hours, or from about 1 hourto about 24 hours. In an aspect, the solidification reaction occurswithin a period of about 10-15 minutes, 15-30 minutes, 15-45 minutes,30-60 minutes, 1 hour-48 hours, 1 hour-24 hours, 1 hour-12 hours, 1hour-11 hours, 1 hour-10 hours, 1 hour-9 hours, 1 hour-8 hours, 1 hour-7hours, 1 hour-6 hours, 1 hour-5 hours, 1 hour-4 hours, 1 hour-3 hours,or 1 hour-2 hours. Without being limited according to the invention, allranges recited are inclusive of the numbers defining the range andinclude each integer within the defined range.

In a preferred aspect, no water is added to the mixing vessel during thestep of mixing at least the biocidal triamine and the acid. In a furtherpreferred aspect, no water is added to the mixing vessel during any stepof the methods of making the solid triamine.

In an aspect, the methods of making the solid triamine, including themixing of the biocidal triamine and acid occur at a temperature for thereaction between about 70° F. (21° C.) and about 130° F. (55° C.).

Solid triamines can be made by merely mixing the biocidal triamine withthe acids in preferred ratios to obtain solid compositions. In an aspectthe ratio of the acid to triamine is from about 1:10 to about 1:1, fromabout 1:10 to about 1:5, from about 1:5 to about 1:3, or from about 1:3to about 1:1. In a further aspect, the ratio of the acid to the triaminecan be any combination below the 1:10 ratio, including for example 1:1,1:0.5, etc. According to the invention the biocidal triamine is thedominant species in the solid compositions. In a preferred aspect, theratio of acid to triamine is from about 1:3 to about 1:2.

The methods of the present invention can produce a stable solid withoutemploying a melt and solidification of the melt as in conventionalcasting. Forming a melt requires heating a composition to melt it. Theheat can be applied externally or can be produced by a chemical exotherm(e.g., from mixing caustic (sodium hydroxide) and water). Heating acomposition consumes energy. Handling a hot melt requires safetyprecautions and equipment. Further, solidification of a melt requirescooling the melt in a container to solidify the melt and form the castsolid. Cooling requires time and/or energy. In contrast, the presentmethod can employ ambient temperature and humidity during solidificationor curing of the solid triamines.

The methods of the present invention can produce a stable solid withoutrequiring extruding to compress the solid triamine through a die.Although extruders could optionally be employed, the solidificationmethods of the invention do not require an extruder. Conventionalprocesses for extruding a mixture through a die to produce a solidcleaning composition apply high pressures to a solid or paste to producethe extruded solid. In contrast, the present method employs pressures onthe solid of less than or equal to about 3000 psi or even as little as 1psi. The solids of the present invention are held together not by merecompression but by compression and/or a binding agent produced in theflowable solid and that is effective for producing a stable solid. In anaspect suitable exemplary binding agents include water, sucrose, citricacid or sodium citrate, polymers and the like, which are not intended tobe limited for the methods of the present invention.

Any of a variety of flowable solids can be used in the method of thepresent invention. For example, in an embodiment, the flowable solid hasa consistency similar to wet sand. Such a flowable solid can becompressed in a person's hand, like forming a snowball. However,immediately after forming it, a forceful impact (dropping or throwing)would return a hand compacted ball of the flowable solid to powder andother smaller pieces. In an embodiment, a flowable solid contains littleenough water that compressing the powder at several hundred psi does notsqueeze liquid water from the solid. In certain embodiments, the presentflowable solid can be a powder or a wetted powder.

Beneficially, the solid triamines of varying solid forms generatedaccording to the methods of the invention are substantially homogeneouswith regard to the distribution of ingredients throughout its mass andare dimensionally stable. As referred to herein, dimensionally stablesolids have less than 3% growth at 104° F., preferably less than 2%growth at 104° F., or preferably less than 3% growth at 122° F. Eachreference to the measurement of dismentional stability is at thementioned temperature and at a relative humidity between about 40 toabout 70%.

Optional Embodiments of Solid Triamines

The methods can further include a step of reducing a water or liquidcontent of the composition for forming the solid triamine and/orincrease the flow of the solid composition. As the preferred aspects donot include adding additional water to the mixing vessel during the stepof mixing at least the biocidal triamine and the acid, furthercomponents can be optionally added to reduce the liquid or water contentof the composition. In an aspect, no water is added to the mixing vesselduring any step of the methods of making the solid triamine. In afurther aspect, an additional agent can be combined with the triamineand the acid to aid in drying out the composition for forming the solidtriamine. In an aspect, a chelant or water sequestrant can be added toeither reduce the water content of solid composition or to aid in flowof the solid triamine composition. In an aspect, a chelant or watersequestrant can be added to the formulation to provide a waterconcentration of less than about 15 wt-%, or less than about 10 wt-%.The reduction of the water or liquid content is particularly well suitedfor pressed solid applications of the making of the solid triamines.

In an aspect, a chelant, such as an aminocarboxylic acid type chelantsor alkali metal salts thereof can be employed, including for example,ethylenediaminetetraacetic acid (EDTA). Other chelants includeN-hydroxyethylaminodiacetic acid; hydroxyethylenediaminetetraaceticacid, nitrilotriacetic acid (NTA);N-hydroxyethyl-ethylenediaminetriacetic acid (HEDTA);diethylenetriaminepentaacetic acid (DTPA); and alanine-N,N-diaceticacid; and the like; and mixtures thereof. Particularly usefulaminocarboxylic acid materials containing little or no NTA and nophosphorus include: N-hydroxyethylaminodiacetic acid,ethylenediaminetetraacetic acid (EDTA),hydroxyethylenediaminetetraacetic acid, diethylenetriaminepentaaceticacid, N-hydroxyethyl-ethylenediaminetriacetic acid (HEDTA),diethylenetriaminepentaacetic acid (DTPA), methylglycinediacetic acid(MGDA), aspartic acid-N,N-diacetic acid (ASDA), glutamicacid-N,N-diacetic acid (GLDA), ethylenediaminesuccinic acid (EDDS),2-hydroxyethyliminodiacetic acid (HEIDA), iminodisuccinic acid (IDS),3-hydroxy-2,2′-iminodisuccinic acid (HIDS) and other similar acidshaving an amino group with a carboxylic acid substituent. Still furtherchelants, including homopolymers and copolymers of polycarboxylic acidsand their partially or completely neutralized salts, monomericpolycarboxylic acids and hydroxycarboxylic acids and their salts can beemployed. Preferred salts of the abovementioned compounds are theammonium and/or alkali metal salts, i.e. the lithium, sodium, andpotassium salts, and particularly preferred salts are the sodium salts,such as sodium sulfate. The chelant concentration in the system incombination with the triamine and acid can range from about about 0 toabout 65 wt-%, 0.1 to about 50 wt-%, about 0.1 to about 50 wt-%, about 1to about 40 wt-%, or about 10 to about 40 wt-% of the composition.Without being limited according to the invention, all ranges recited areinclusive of the numbers defining the range and include each integerwithin the defined range.

The methods can further include a step of pelletizing the solid triamineraw material. Pelletizing can further include compressing the solidgranular or agglomerated solid triamines in appropriate pelletizingequipment to result in appropriately sized pelletized materials.

The methods can further include a step of introducing the solid triamineraw material into a container to form a solid block and/or cast solidblock. Preferred containers include disposable plastic containers orwater soluble film containers. Other suitable packaging for the solidtriamines includes flexible bags, packets, shrink wrap, and watersoluble film such as polyvinyl alcohol.

The methods can further include a step of extruding the solid triaminesafter the mixing step. In an extrusion step, the solid triamines aredischarged from the mixing system into, or through, a die or othershaping means. The product is then packaged. In an exemplary embodiment,the formed solid triamines begins to harden to a solid form in betweenapproximately 1 minute and approximately 3 hours. Particularly, theformed solid triamines begins to harden to a solid form in betweenapproximately 1 minute and approximately 2 hours. More particularly, theformed solid triamines begins to harden to a solid form in betweenapproximately 1 minute and approximately 20 minutes.

The methods can further include a step of casting the solid triaminesafter the mixing step. In an exemplary embodiment, the solid triaminesare transferred to a packaging container where solidification takesplace. In an exemplary embodiment, the cast solid triamines begins toharden to a solid form in between approximately 15 minutes to 48 hours,10-15 minutes, 15-30 minutes, 15-45 minutes, 30-60 minutes, 1 hour-48hours, 1 hour-24 hours, 1 hour-12 hours, 1 hour-11 hours, 1 hour-10hours, 1 hour-9 hours, 1 hour-8 hours, 1 hour-7 hours, 1 hour-6 hours, 1hour-5 hours, 1 hour-4 hours, 1 hour-3 hours, or 1 hour-2 hours.Particularly, the cast solid triamines begins to harden to a solid formin between approximately 15 minutes and approximately 24 or 48 hours.More particularly, the cast solid triamines begins to harden to a solidform in between approximately 1 minute and approximately 20 minutes.

The methods can further include a step of pressing the solid triamines.In a pressed solid triamine process, the solid triamines are combinedunder pressure. In a pressed solid process, flowable triamine solids areplaced into a form (e.g., a mold or container). The method can includegently pressing the flowable solid in the form to produce the pressedsolid triamines. Pressure may be applied by a block machine or aturntable press, or the like. Pressure may be applied at ranges fromabout 1 to about 3000 psi, or about 1 to about 1000 psi depending uponthe block shape and cylinder pressure. In certain embodiments, themethods can employ pressures as low as greater than or equal to about 1psi, greater than or equal to about 2, greater than or equal to about 5psi, or greater than or equal to about 10 psi. As used herein, the term“psi” or “pounds per square inch” refers to the actual pressure appliedto the flowable solid being pressed and does not refer to the gauge orhydraulic pressure measured at a point in the apparatus doing thepressing.

The method can further include a curing step to produce the solidtriamines. As referred to herein, an uncured solid triamine includingthe flowable solid is compressed to provide sufficient surface contactbetween particles making up the flowable solid that the uncuredcomposition will solidify into a stable solid. A sufficient quantity ofparticles (e.g. granules) in contact with one another provides bindingof particles to one another effective for making a stable solidcomposition. Inclusion of a curing step may include allowing the pressedsolid to solidify for a period of time, such as a few hours, or about 1day (or longer). In additional aspects, the methods could includevibrating the flowable solid in the form or mold, such as the methodsdisclosed in U.S. Pat. No. 8,889,048, which is herein incorporated byreference in its entirety.

Solid Triamine Compositions

The solid triamines disclosed pursuant to the invention are furthersuitable for use in formulating various solid triamine compositions.Exemplary ranges of the solid triamine compositions according to theinvention are shown in Tables 2A-2C in weight percentage of the solidcompositions.

TABLE 2A First Second Third Fourth Exemplary Exemplary ExemplaryExemplary Material Range wt-% Range wt-% Range wt-% Range wt-% Triamine10-99  20-90 50-90  10-50 Solid acid 1-60 2.5-40  5-40 2.5-20 Additional 0-65  0-25 0-15 15-50 Functional Ingredients (e.g. chelants,enzymes)

TABLE 2B First Second Third Exemplary Exemplary Exemplary Material Rangewt-% Range wt-% Range wt-% Triamine 10-99  20-90 50-90  Solid acid 1-502.5-40  5-40 Additional Functional 0-65  0-50 0-40 Ingredients Enzymes0.01-10   0.1-10  0.1-5

TABLE 2C First Second Third Exemplary Exemplary Exemplary Material Rangewt-% Range wt-% Range wt-% Triamine 10-99  10-80  10-50 Solid acid 1-502.5-40   2.5-20  Additional Functional 0-55 0-25  0-15 IngredientsChelant 0.1-65   1-60 10-60

Further exemplary ranges of the solid triamine compositions particularlysuitable for antimicrobial, sanitizing and disinfectant compositionsaccording to the invention are shown in Tables 3A-3C in weightpercentage of the solid compositions.

TABLE 3A First Second Third Exemplary Exemplary Exemplary Material Rangewt-% Range wt-% Range wt-% Triamine 10-99  10-70 20-50 Solid acid 1-502.5-40   5-20 Additional Functional 0-90 10-80 20-75 Ingredients (e.g.chelant, enzymes)

TABLE 3B First Second Third Exemplary Exemplary Exemplary Material Rangewt-% Range wt-% Range wt-% Triamine 10-99  10-70 20-50 Solid acid 1-502.5-40   5-20 Additional Functional 0-90 10-80 20-75 Ingredients Enzymes0.01-10   0.1-10  0.1-5  

TABLE 3C First Second Third Exemplary Exemplary Exemplary Material Rangewt-% Range wt-% Range wt-% Triamine 10-99  10-70 20-50 Solid acid 1-502.5-40   5-20 Additional Functional 0-90 10-80 20-75 Ingredients Chelant0.1-65    1-60 10-60

Beneficially, the solid triamine compositions are at least partiallyneutralized, allowing activity of 90% and greater of the biocidaltriamine, and provide at least substantially similar or superiorperformance and micro efficacy to liquid formulations.

The solid compositions may be provided in varying sizes and may besuitable for single or multiple use applications. In an exemplaryaspect, the total weight of a single dosage use form of said solidcomposition of the present invention can be for example ≧0.005 kg to <1kg, preferably ≧0.005 kg to <0.25 kg. In a further exemplary aspect, thetotal weight of a multiple use form of said solid composition of thepresent invention can be for example ≧0.5 kg to <15 kg, preferably ≧1 kgto <10 kg.

In an aspect the ratio of the acid to triamine is from about 1:10 toabout 1:1, from about 1:10 to about 1:5, from about 1:5 to about 1:3, orfrom about 1:3 to about 1:1. In a further aspect, the ratio of the acidto the triamine can be any combination below the 1:10 ratio, includingfor example 1:1, 1:0.5, etc. According to the invention the biocidaltriamine is the dominant species in the solid compositions. In apreferred aspect, the ratio of acid to triamine is from about 1:3 toabout 1:2. Without being limited to a particular mechanism of action theratio of triamine to acid impacts the stability of the solid compositiongenerated. In an aspect, a higher acid concentration results in agreater water content from the neutralization step in the generatedsolid biocidal triamine composition and may impact the type of solidgenerated. For example, a solid biocidal triamine composition having alower water content is optimal for producing pressed solids according tothe invention. However, solid biocidal triamine compositions havingincreased water content remain suitable for use in pressed, cast and/orextruded solids.

According to embodiments of the invention, the solid triaminecompositions are partially neutralized compositions. In an aspect, thesolid compositions have a pH from about 6 to about 11, from about 6.5 toabout 9.5, and preferably from about 7 to about 9 or about 7. In anaspect of the invention more acidic compositions (pH below 7) achievestable solid compositions using a higher acid concentration. In yetother aspects, lower concentrations of acid (providing a pH of at least8) is preferred for optimal micro efficacy.

The degree of hardness of the solid compositions generated according tothe invention may range from that of a flowable or free-flowing powderto a fused solid product which is relatively dense and hard, to aconsistency characterized as being a hardened paste. In addition, theterm “solid” refers to the state of the triamine composition under theexpected conditions of storage and use of the solid triaminecomposition. In general, it is expected that the solid triaminecomposition will remain in solid form when exposed to temperatures of upto approximately 100° F. and preferably up to approximately 122° F.

According to the embodiments of the invention the solid triaminecompositions can be utilized for any pressed, extruded and/or cast solidcompositions. Still further, according to the invention the compositioncan be utilized for any molded or formed solid pellet, block, tablet,powder, granule, flake or the formed solid can thereafter be ground orformed into a powder, granule, or flake.

Water

The solid composition according to the present invention can contain asmall amount of water. For example, components of the solid compositionsuch as the biocidal triamine (or other functional ingredients) maycomprise water. Preferably water is not added into the composition andbased on the total weight of the solid composition there is a watercontent in the range of ≧0 wt-% to <5 wt-%, preferably ≧0 wt-% to <2.5wt-%, further preferred ≧0 wt-% to <1 wt-%, furthermore preferred ≧0wt-% to <0.01 wt-%. In some aspects, including those where additionalfunctional ingredients are included in the formulations, components withadditional water content can be included in the composition, andpreferably total water content of the solid formulations is less thanabout 10 wt-%, less than about 9 wt-%, less than about 8 wt-%, less thanabout 7.5 wt-%, less than about 7 wt-%, less than about 6 wt-%, or lessthan about 5 wt-%. Without being limited according to the invention, allranges recited are inclusive of the numbers defining the range andinclude each integer within the defined range.

Additional Functional Ingredients

The components of the solid triamine compositions can optionally becombined with various functional components suitable for use indisinfectant applications. In some embodiments few or no additionalfunctional ingredients are disposed therein the solid triaminecompositions. In other embodiments, the solid triamine compositionsinclude at least one additional functional ingredient. Additionalfunctional ingredients provide desired properties and functionalities tothe compositions. For the purpose of this application, the term“functional ingredient” includes a material that when formulated intothe solid composition or when dispersed or dissolved in a use and/orconcentrate solution of the solid triamine compositions, provides abeneficial property in a particular disinfectant application of use.Additional functional ingredients may provide formulation benefitsand/or performance benefits.

Some particular examples of functional materials are discussed in moredetail below, although the particular materials discussed are given byway of example only, and that a broad variety of other functionalingredients may be used. For example, many of the functional materialsdiscussed below relate to materials used in cleaning and disinfectantapplications. However, other embodiments may include functionalingredients for use in other applications. In preferred embodiments, thecompositions do not include or are substantially free of boric acid orboric acid salts.

In other embodiments, the solid triamine compositions may includeenzymes, additional hardening or solidifying agents, defoaming agents,anti-redeposition agents, bleaching agents, solubility modifiers,dispersants, rinse aids, metal protecting agents, stabilizing agents,corrosion inhibitors, additional sequestrants and/or chelating agents,fragrances and/or dyes, rheology modifiers or thickeners, hydrotropes orcouplers, buffers, solvents and the like.

In some aspects, the solid triamine compositions include from about 0wt-% to about 50 wt-% additional functional ingredients, from about 0wt-% to about 25 wt-% additional functional ingredients, or from about 0wt-% to about 15 wt-% additional functional ingredients. In a preferredaspect, the solid triamine compositions including substantial amounts ofadditional functional ingredients for suitable antimicrobial, sanitizingand disinfectant compositions include from about 0 wt-% to about 90 wt-%additional functional ingredients, from about 10 wt-% to about 80 wt-%additional functional ingredients, or from about 20 wt-% to about 75wt-% additional functional ingredients. Without being limited accordingto the invention, all ranges recited are inclusive of the numbersdefining the range and include each integer within the defined range.

Enzymes

In some embodiments, the solid triamine compositions may further includean enzyme, but may include any number of enzymes. The enzyme may includea protease, amylase, lipase, gluconase, cellulase, peroxidase, acombination, or other enzymes. The system preferably includes at leastone lipase. The enzymes may be vegetable, animal, bacterial, fungal oryeast enzymes, or genetic variations thereof. The enzyme should beselected based on factors like pH, stability, temperature, andcompatibility with materials found in detergent compositions andcleaning applications. Preferred enzymes have activity in the pH rangeof about 2-14 or 6-12 and at temperatures from about 20.degree. C. to80.degree. C. The enzyme may be a wild type enzyme or a recombinantenzyme. Preferred enzymes have a broad spectrum of activity and a hightolerance for materials found in cleaning compositions like alkalinity,acidity, chelating agents, sequestering agents, and surfactants.

The enzyme concentration in the system depends on the particularenzyme's activity. The enzyme concentration can range from about 0 toabout 10.0 wt-%, about 0.1 to about 5.0 wt-%, or about 0.5 to about 2.0wt-% of a commercially available enzyme product. Without being limitedaccording to the invention, all ranges recited are inclusive of thenumbers defining the range and include each integer within the definedrange. A person skilled in the art will be able to determine the enzymeconcentration after selecting a desired enzyme based on the enzyme'sactivity and profile.

Exemplary enzymes are listed below, and description of the same isincorporated by reference in its entirety with respect to exemplaryenzymes from U.S. Pat. No. 8,211,849:

Lipase

Lipase isolated from: Pseudomona, Pseudomonas stutzeri ATCC 19.154,Humicola, Humicola lanuginose (reproduced recombinantly in Aspergillusoryzae), Chromobacter viscosum, Pseudomonas gladioli, Humicolalanuginose, and the like.

Protease

Protease isolated from: Bacillus lentus, Bacillus licheniformis,Bacillus amyloliquefaciens, and the like.

Amylase

Amylase isolated from: Bacillus licheniformis, Bacillusamyloliquefaciens, Bacillus subtilis, Bacillus stearothermophilus, andthe like.

Cellulase

Cellulase isolated from: Humicola insolens, Humicola strain DSM 1800,cellulase 212-producing fungus of the genus Aeromonas, cellulaseextracted from the hepatopancrease of the marine mollusk DorabellaAuricula Solander, and the like.

Other Enzymes

Peroxidase (horseradish peroxidase)

Ligninase

Haloperoxidase (chloroperoxidase, bromoperoxidase)

Gluconase

Chelants

In some embodiments, the solid triamine compositions may further includea chelant. Chelation herein means the binding or complexation of a bi-or multidentate ligand. These ligands, which are often organiccompounds, are called chelants, chelators, chelating agents, and/orsequestering agent. Chelating agents form multiple bonds with a singlemetal ion. Chelants, are chemicals that form soluble, complex moleculeswith certain metal ions, inactivating the ions so that they cannotnormally react with other elements or ions to produce precipitates orscale. The ligand forms a chelate complex with the substrate. The termis reserved for complexes in which the metal ion is bound to two or moreatoms of the chelant.

Suitable aminocarboxylic acid type chelants include the acids, or alkalimetal salts thereof. Some examples of aminocarboxylic acid materialsinclude amino acetates and salts thereof. Some examples include thefollowing: N-hydroxyethylaminodiacetic acid;hydroxyethylenediaminetetraacetic acid, nitrilotriacetic acid (NTA);ethylenediaminetetraacetic acid (EDTA);N-hydroxyethyl-ethylenediaminetriacetic acid (HEDTA);diethylenetriaminepentaacetic acid (DTPA); and alanine-N,N-diaceticacid; and the like; and mixtures thereof. Particularly usefulaminocarboxylic acid materials containing little or no NTA and nophosphorus include: N-hydroxyethylaminodiacetic acid,ethylenediaminetetraacetic acid (EDTA),hydroxyethylenediaminetetraacetic acid, diethylenetriaminepentaaceticacid, N-hydroxyethyl-ethylenediaminetriacetic acid (HEDTA),diethylenetriaminepentaacetic acid (DTPA), methylglycinediacetic acid(MGDA), aspartic acid-N,N-diacetic acid (ASDA), glutamicacid-N,N-diacetic acid (GLDA), ethylenediaminesuccinic acid (EDDS),2-hydroxyethyliminodiacetic acid (HEIDA), iminodisuccinic acid (IDS),3-hydroxy-2,2′-iminodisuccinic acid (HIDS) and other similar acidshaving an amino group with a carboxylic acid substituent.

Other chelants include amino carboxylates include ethylenediaminetetra-acetates, N-hydroxyethylethylenediaminetriacetates,nitrilo-triacetates, ethylenediamine tetrapro-prionates,triethylenetetraaminehexacetates, diethylenetriaminepentaacetates, andethanoldi-glycines, alkali metal, ammonium, and substituted ammoniumsalts therein and mixtures therein. Suitable chelating agents can beselected from the group consisting of amino carboxylates, aminophosphonates, polyfunctionally-substituted aromatic chelating agents andmixtures thereof. Exemplary chelants include amino acids based chelantsand preferably citrate, tartrate, and glutamic-N,N-diacetic acid andderivatives and/or phosphonate based chelants.

Other chelants include homopolymers and copolymers of polycarboxylicacids and their partially or completely neutralized salts, monomericpolycarboxylic acids and hydroxycarboxylic acids and their salts.Preferred salts of the abovementioned compounds are the ammonium and/oralkali metal salts, i.e. the lithium, sodium, and potassium salts, andparticularly preferred salts are the sodium salts, such as sodiumsulfate.

Other compounds suitable for use as additional functional ingredients toreduce the water conent of the solid composition may include sodiumacetate and other anti-caking agents. These may be necessary due to theconcentration of water introduced to the solid compositions by way ofchelants, such as EDTA. In a preferred aspect, the additional functionalingredient is employed to reduce the total water content of the solidcomposition to less than about 10 wt-%, less than about 9 wt-%, lessthan about 8 wt-%, less than about 7.5 wt-%, less than about 7 wt-%,less than about 6 wt-%, or less than about 5 wt-% water. The chelantconcentration in the system can range from about about 0 to about 65wt-%, 0.1 to about 50 wt-%, about 0.1 to about 50 wt-%, about 1 to about40 wt-%, or about 10 to about 40 wt-% of the composition. Without beinglimited according to the invention, all ranges recited are inclusive ofthe numbers defining the range and include each integer within thedefined range.

Defoaming Agents

In some embodiments, the solid triamine compositions may further includean additive like an antifoam agent. The antifoam agent is preferablyselected from the variety of antifoams such as those of the silicon typeand/or polypropylene glycol type. Antifoam agents can be selected fromthe group comprising silicones and/or other defoamers like defoamingsurfactants. Suitable silicone based antifoam agents have a siliconecompound as the active component. These are delivered as oil or a waterbased emulsion. The silicone compound consists preferably of anhydrophobic silica dispersed in a silicone oil. The silicone compoundmight also contain silicone glycols and other modified silicone fluids.Suitable ethylene glycol (EO) and/or propylene glycol (PO) basedantifoam agents contain polyethylene glycol and polypropylene glycolcopolymers. They are delivered as oils, water solutions, or water basedemulsions. EO/PO copolymers normally have good dispersing properties.

The defoaming agent concentration in the system can range from about 0to about 50 wt-%, about 0.01 to about 30 wt-%, or about 0.1 to about 30wt-%. Without being limited according to the invention, all rangesrecited are inclusive of the numbers defining the range and include eachinteger within the defined range.

Surfactants

In some embodiments, the solid triamine compositions may further includea surfactant. Surfactants suitable for use with the compositions of thepresent invention include, but are not limited to, nonionic surfactants,cationic surfactants, and anionic surfactants based upon the solubilityof the biocidal triamines In some embodiments, the solid triaminecompositions of the present invention include about 0 wt-% to about 50wt-% of a surfactant, from about 5 wt-% to about 25 wt-% of asurfactant, or from about 5 wt-% to about 15 wt-% of a surfactant.Without being limited according to the invention, all ranges recited areinclusive of the numbers defining the range and include each integerwithin the defined range.

Nonionic Surfactants

Suitable nonionic surfactants suitable for use with the compositions ofthe present invention include alkoxylated surfactants. Suitablealkoxylated surfactants include EO/PO copolymers, capped EO/POcopolymers, alcohol alkoxylates, capped alcohol alkoxylates, mixturesthereof, or the like. Suitable alkoxylated surfactants for use assolvents include EO/PO block copolymers, such as the Pluronic andreverse Pluronic surfactants; alcohol alkoxylates, such as Dehypon LS-54(R-(EO)₅(PO)₄) and Dehypon LS-36 (R-(EO)₃(PO)₆); and capped alcoholalkoxylates, such as Plurafac LF221 and Tegoten EC11; mixtures thereof,or the like.

The semi-polar type of nonionic surface active agents is another classof nonionic surfactant useful in compositions of the present invention.Semi-polar nonionic surfactants include the amine oxides, phosphineoxides, sulfoxides and their alkoxylated derivatives.

Amine oxides are tertiary amine oxides corresponding to the generalformula:

wherein the arrow is a conventional representation of a semi-polar bond;and, R¹, R², and R³ may be aliphatic, aromatic, heterocyclic, alicyclic,or combinations thereof. Generally, for amine oxides of detergentinterest, R¹ is an alkyl radical of from about 8 to about 24 carbonatoms; R² and R³ are alkyl or hydroxy alkyl of 1-3 carbon atoms or amixture thereof R² and R³ can be attached to each other, e.g. through anoxygen or nitrogen atom, to form a ring structure; R⁴ is an alkylene ora hydroxy alkylene group containing 2 to 3 carbon atoms; and n rangesfrom 0 to about 20. An amine oxide can be generated from thecorresponding amine and an oxidizing agent, such as hydrogen peroxide.

Useful water soluble amine oxide surfactants are selected from theoctyl, decyl, dodecyl, isododecyl, coconut, or tallow alkyl di-(loweralkyl) amine oxides, specific examples of which are octyldimethylamineoxide, nonyldimethylamine oxide, decyldimethylamine oxide,undecyldimethylamine oxide, dodecyldimethylamine oxide,iso-dodecyldimethyl amine oxide, tridecyldimethylamine oxide,tetradecyldimethylamine oxide, pentadecyldimethylamine oxide,hexadecyldimethylamine oxide, heptadecyldimethylamine oxide,octadecyldimethylaine oxide, dodecyldipropylamine oxide,tetradecyldipropylamine oxide, hexadecyldipropylamine oxide,tetradecyldibutylamine oxide, octadecyldibutylamine oxide,bis(2-hydroxyethyl)dodecylamine oxide,bis(2-hydroxyethyl)-3-dodecoxy-1-hydroxypropylamine oxide,dimethyl-(2-hydroxydodecyl)amine oxide, 3,6,9-trioctadecyldimethylamineoxide and 3-dodecoxy-2-hydroxypropyldi-(2-hydroxyethyl)amine oxide.

Functional Siloxane Surfactants

The composition can also optionally include one or more functionalpolysiloxanes. For example, in some embodiments, a polyalkyleneoxide-modified polydimethylsiloxane, nonionic surfactant or apolybetaine-modified polysiloxane amphoteric surfactant can be employedas an additive. Both, in some embodiments, are linear polysiloxanecopolymers to which polyethers or polybetaines have been grafted througha hydrosilation reaction. Some examples of specific siloxane surfactantsare known as SILWET® surfactants available from Union Carbide, ABIL®polyether or polybetaine polysiloxane copolymers available from EvonikCorporation, Tegopren® polyether polysiloxane copolymers available fromEvonik Corporation and others described in U.S. Pat. No. 4,654,161 whichis incorporated herein by reference. Preferred functional siloxanesurfactants include, but are not limited Tegopren® 5831, Tegopren® 5840,Tegopren® 5847, Tegopren® 5852 and Tegopren® 5853. In some embodiments,the particular siloxanes used can be described as having, e.g., lowsurface tension, high wetting ability and excellent lubricity. Forexample, these surfactants are said to be among the few capable ofwetting polytetrafluoroethylene surfaces. The siloxane surfactantemployed as an additive can be used alone or in combination with afluorochemical surfactant. In some embodiments, the fluorochemicalsurfactant employed as an additive optionally in combination with asilane, can be, for example, a nonionic fluorohydrocarbon, for example,fluorinated alkyl polyoxyethylene ethanols, fluorinated alkyl alkoxylateand fluorinated alkyl esters. Further description of such functionalpolydimethylsiloxones and/or fluorochemical surfactants are described inU.S. Pat. Nos. 5,880,088; 5,880,089; and 5,603,776, all of which patentsare incorporated herein by reference.

In some embodiments, the composition may include functionalpolydimethylsiloxones in an amount in the range of up to about 10 wt.-%.For example, some embodiments may include in the range of about 0.1 toabout 10 wt.-% of a polyalkylene oxide-modified polydimethylsiloxane ora polybetaine-modified polysiloxane, optionally in combination withabout 0.1 to about 10 wt.-% of a fluorinated hydrocarbon nonionicsurfactant.

Anionic Surfactants

Anionic sulfate surfactants suitable for use in the present compositionsinclude alkyl ether sulfates, alkyl sulfates, the linear and branchedprimary and secondary alkyl sulfates, alkyl ethoxysulfates, fatty oleylglycerol sulfates, alkyl phenol ethylene oxide ether sulfates, theC₅-C₁₇ acyl-N 3(C₁-C₄ alkyl) and —N—(C₁-C₂ hydroxyalkyl) glucaminesulfates, and sulfates of alkylpolysaccharides such as the sulfates ofalkylpolyglucoside, and the like. Also included are the alkyl sulfates,alkyl poly(ethyleneoxy) ether sulfates and aromatic poly(ethyleneoxy)sulfates such as the sulfates or condensation products of ethylene oxideand nonyl phenol (usually having 1 to 6 oxyethylene groups permolecule).

Anionic sulfonate surfactants suitable for use in the presentcompositions also include alkyl sulfonates, the linear and branchedprimary and secondary alkyl sulfonates, and the aromatic sulfonates withor without substituents.

Anionic carboxylate surfactants suitable for use in the presentcompositions include carboxylic acids (and salts), such as alkanoicacids (and alkanoates), ester carboxylic acids (e.g. alkyl succinates),ether carboxylic acids, and the like. Such carboxylates include alkylethoxy carboxylates, alkyl aryl ethoxy carboxylates, alkyl polyethoxypolycarboxylate surfactants and soaps (e.g. alkyl carboxyls). Secondarycarboxylates useful in the present compositions include those whichcontain a carboxyl unit connected to a secondary carbon. The secondarycarbon can be in a ring structure, e.g. as in p-octyl benzoic acid, oras in alkyl-substituted cyclohexyl carboxylates. The secondarycarboxylate surfactants typically contain no ether linkages, no esterlinkages and no hydroxyl groups. Further, they typically lack nitrogenatoms in the head-group (amphiphilic portion). Suitable secondary soapsurfactants typically contain 11-13 total carbon atoms, although morecarbons atoms (e.g., up to 16) can be present. Suitable carboxylatesalso include acylamino acids (and salts), such as acylgluamates, acylpeptides, sarcosinates (e.g. N-acyl sarcosinates), taurates (e.g. N-acyltaurates and fatty acid amides of methyl tauride), and the like.

Suitable anionic surfactants include alkyl or alkylaryl ethoxycarboxylates of the following formula:

R—O—(CH₂CH₂O)_(n)(CH₂)_(m)—CO₂X   (3)

in which R is a C₈ to C₂₂ alkyl group or

in which R¹ is a C₄-C₁₆ alkyl group; n is an integer of 1-20; m is aninteger of 1-3; and X is a counter ion, such as hydrogen, sodium,potassium, lithium, ammonium, or an amine salt such as monoethanolamine,diethanolamine or triethanolamine. In some embodiments, n is an integerof 4 to 10 and m is 1. In some embodiments, R is a C₈-C₁₆ alkyl group.In some embodiments, R is a C₁₂-C₁₄ alkyl group, n is 4, and m is 1.

In other embodiments, R is

and R¹ is a C₆-C₁₂ alkyl group. In still yet other embodiments, R¹ is aC₉ alkyl group, n is 10 and m is 1.

Such alkyl and alkylaryl ethoxy carboxylates are commercially available.These ethoxy carboxylates are typically available as the acid forms,which can be readily converted to the anionic or salt form. Commerciallyavailable carboxylates include, Neodox 23-4, a C₁₂₋₁₃ alkyl polyethoxy(4) carboxylic acid (Shell Chemical), and Emcol CNP-110, a C₉ alkylarylpolyethoxy (10) carboxylic acid (Witco Chemical). Carboxylates are alsoavailable from Clariant, e.g. the product Sandopan® DTC, a C₁₃ alkylpolyethoxy (7) carboxylic acid.

Cationic Surfactants

Cationic surfactants preferably include, more preferably refer to,compounds containing at least one long carbon chain hydrophobic groupand at least one positively charged nitrogen. The long carbon chaingroup may be attached directly to the nitrogen atom by simplesubstitution; or more preferably indirectly by a bridging functionalgroup or groups in so-called interrupted alkylamines and amido amines.Such functional groups can make the molecule more hydrophilic and/ormore water dispersible, more easily water solubilized by co-surfactantmixtures, and/or water soluble. For increased water solubility,additional primary, secondary or tertiary amino groups can be introducedor the amino nitrogen can be quaternized with low molecular weight alkylgroups. Further, the nitrogen can be a part of branched or straightchain moiety of varying degrees of unsaturation or of a saturated orunsaturated heterocyclic ring. In addition, cationic surfactants maycontain complex linkages having more than one cationic nitrogen atom.

The surfactant compounds classified as amine oxides, amphoterics andzwitterions are themselves typically cationic in near neutral to acidicpH solutions and can overlap surfactant classifications.Polyoxyethylated cationic surfactants generally behave like nonionicsurfactants in alkaline solution and like cationic surfactants in acidicsolution.

The simplest cationic amines, amine salts and quaternary ammoniumcompounds can be schematically drawn thus:

in which, R represents a long alkyl chain, R′, R″, and R′″ may be eitherlong alkyl chains or smaller alkyl or aryl groups or hydrogen and Xrepresents an anion. The amine salts and quaternary ammonium compoundsare preferred for practical use in this invention due to their highdegree of water solubility.

The majority of large volume commercial cationic surfactants can besubdivided into four major classes and additional sub-groups known tothose or skill in the art and described in “Surfactant Encyclopedia”,Cosmetics & Toiletries, Vol. 104 (2) 86-96 (1989). The first classincludes alkylamines and their salts. The second class includes alkylimidazolines. The third class includes ethoxylated amines. The fourthclass includes quaternaries, such as alkylbenzyldimethylammonium salts,alkyl benzene salts, heterocyclic ammonium salts, tetra alkylammoniumsalts, and the like. Cationic surfactants are known to have a variety ofproperties that can be beneficial in the present compositions. Thesedesirable properties can include detergency in compositions of or belowneutral pH, antimicrobial efficacy, thickening or gelling in cooperationwith other agents, and the like.

Cationic surfactants useful in the compositions of the present inventioninclude those having the formula R¹ _(m)R² _(x)Y_(L)Z wherein each R¹ isan organic group containing a straight or branched alkyl or alkenylgroup optionally substituted with up to three phenyl or hydroxy groupsand optionally interrupted by up to four of the following structures:

or an isomer or mixture of these structures, and which contains fromabout 8 to 22 carbon atoms. The R¹ groups can additionally contain up to12 ethoxy groups. m is a number from 1 to 3. Preferably, no more thanone R¹ group in a molecule has 16 or more carbon atoms when m is 2 ormore than 12 carbon atoms when m is 3. Each R² is an alkyl orhydroxyalkyl group containing from 1 to 4 carbon atoms or a benzyl groupwith no more than one R² in a molecule being benzyl, and x is a numberfrom 0 to 11, preferably from 0 to 6. The remainder of any carbon atompositions on the Y group are filled by hydrogens. Y is can be a groupincluding, but not limited to:

or a mixture thereof Preferably, L is 1 or 2, with the Y groups beingseparated by a moiety selected from R¹ and R² analogs (preferablyalkylene or alkenylene) having from 1 to about 22 carbon atoms and twofree carbon single bonds when L is 2. Z is a water soluble anion, suchas a halide, sulfate, methylsulfate, hydroxide, or nitrate anion,particularly preferred being chloride, bromide, iodide, sulfate ormethyl sulfate anions, in a number to give electrical neutrality of thecationic component.

Hardening Agents

The solid compositions can also include a hardening agent to be employedwith the solid triamines. A hardening agent is a compound or system ofcompounds, organic or inorganic, which significantly contributes to theuniform solidification of the composition. Preferably, the hardeningagents are compatible with the cleaning agent and other activeingredients of the composition and are capable of providing an effectiveamount of hardness and/or aqueous solubility to the processedcomposition. The hardening agents should also be capable of forming ahomogeneous matrix with the cleaning agent and other ingredients whenmixed and solidified to provide a uniform dissolution of the cleaningagent from the solid detergent composition during use.

The amount of hardening agent included in the solid compositions willvary according to factors including, but not limited to: the type ofsolid composition being prepared, the ingredients of the solidcomposition, the intended use of the composition, the quantity ofdispensing solution applied to the solid composition over time duringuse, the temperature of the dispensing solution, the hardness of thedispensing solution, the physical size of the solid composition, theconcentration of the other ingredients, and the concentration of thesolid triamines in the composition. It is preferred that the amount ofthe hardening agent included in the solid composition is effective tocombine with the solid triamines and other ingredients of thecomposition to form a homogeneous mixture under continuous mixingconditions and a temperature at or below the melting temperature of thehardening agent.

The hardening agent may be an organic or an inorganic hardening agent. Apreferred organic hardening agent is a polyethylene glycol (PEG)compound. The solidification rate of solid compositions comprising apolyethylene glycol hardening agent will vary, at least in part,according to the amount and the molecular weight of the polyethyleneglycol added to the composition. Examples of suitable polyethyleneglycols include, but are not limited to: solid polyethylene glycols ofthe general formula H(OCH₂CH₂)_(n)OH, where n is greater than 15,particularly approximately 30 to approximately 1700. Typically, thepolyethylene glycol is a solid in the form of a free-flowing powder orflakes, having a molecular weight of approximately 1,000 toapproximately 100,000, particularly having a molecular weight of atleast approximately 1,450 to approximately 20,000, more particularlybetween approximately 1,450 to approximately 8,000. The polyethyleneglycol is present at a concentration of from approximately 0% to 75% byweight and particularly approximately 0.1% to approximately 15% byweight.

Inorganic hardening agents are hydratable inorganic salts, including,but not limited to: sulfates and bicarbonates. The inorganic hardeningagents are present at concentrations of up to approximately 50% byweight, particularly approximately 5% to approximately 25% by weight,and more particularly approximately 5% to approximately 15% by weight.Urea particles can also be employed as hardeners in the solidcompositions. The solidification rate of the compositions will vary, atleast in part, to factors including, but not limited to: the amount, theparticle size, and the shape of the urea added to the composition. Forexample, a particulate form of urea can be combined with a cleaningagent and other ingredients, and preferably a minor but effective amountof water. The amount and particle size of the urea is effective tocombine with the cleaning agent and other ingredients to form ahomogeneous mixture without the application of heat from an externalsource to melt the urea and other ingredients to a molten stage. It ispreferred that the amount of urea included in the solid composition iseffective to provide a desired hardness and desired rate of solubilityof the composition when placed in an aqueous medium to achieve a desiredrate of dispensing the cleaning agent from the solidified compositionduring use. In some embodiments, the composition includes betweenapproximately 0% to approximately 90% by weight urea, particularlybetween approximately 5% and approximately 40% by weight urea, and moreparticularly between approximately 10% and approximately 30% by weighturea. The urea may be in the form of prilled beads or powder. Prilledurea is generally available from commercial sources as a mixture ofparticle sizes ranging from about 8-15 U.S. mesh, as for example, fromArcadian Sohio Company, Nitrogen Chemicals Division. A prilled form ofurea is preferably milled to reduce the particle size to about 50 U.S.mesh to about 125 U.S. mesh, particularly about 75-100 U.S. mesh,preferably using a wet mill such as a single or twin-screw extruder, aTeledyne mixer, a Ross emulsifier, and the like.

Methods of Making

Solid triamine compositions are produced according to the methods of theinvention. In an aspect, it is beneficial to formulate and deliver asolid composition for numerous reasons, including reduction of storagespace and transport costs. In some aspects, the volume of the solidcomposition compared to a concentrated liquid equivalent can be reducedfor example to at least 80%. Another object of the present invention isdirected to a method of manufacture of a solid composition of thepresent invention. All components that can be used in that process ofmanufacture are already defined for the solid composition of the presentinvention.

In an aspect, the triamine solids are made by a process comprisingmixing at least the biocidal triamine and the acid to neutralize thebiocidal triamine to a pH from about 7 to about 10. The neutralizationoccurs during the mixing of the components in a mixing vessel. In anaspect, the alkaline pH of the biocidal triamine is neutralized prior tothe solidification. In an aspect, the solidification reaction occursover a period from about 1 hour to about 48 hours, or from about 1 hourto about 24 hours. In a preferred aspect, no water is added to themixing vessel and the temperature for the reaction is between about 70°F. (21° C.) and about 130° F. (55° C.). In an aspect, mixing thecomponents includes preferably mixing until a homogeneous mixture isobtained.

As one skilled in the art will ascertain, the mixing of the components,including the biocidal triamine and the acid, along with any number ofoptional additional functional ingredients, may include varioussequences of adding the components to obtain the mixture. The methods ofgenerating the solid compositions are not intended to be limitedaccording to alterations in the process of manufacture involving theorder of mixing the components described herein.

The methods of the present invention can produce a stable solid withoutemploying a melt and solidification of the melt as in conventionalcasting. Forming a melt requires heating a composition to melt it. Theheat can be applied externally or can be produced by a chemical exotherm(e.g., from mixing caustic (sodium hydroxide) and water). Heating acomposition consumes energy. Handling a hot melt requires safetyprecautions and equipment. Further, solidification of a melt requirescooling the melt in a container to solidify the melt and form the castsolid. Cooling requires time and/or energy. In contrast, the presentmethod can employ ambient temperature and humidity during solidificationor curing of the present compositions.

The methods of the present invention can produce a stable solid withoutextruding to compress the mixture through a die. Conventional processesfor extruding a mixture through a die to produce a solid cleaningcomposition apply high pressures to a solid or paste to produce theextruded solid. In contrast, the present method employs pressures on thesolid of less than or equal to about 3000 psi or even as little as 1psi. The solids of the present invention are held together not by merecompression but by a binding agent produced in the flowable solid andthat is effective for producing a stable solid.

Any of a variety of flowable solids can be used in the method of thepresent invention. For example, in an embodiment, the flowable solid hasa consistency similar to wet sand. Such a flowable solid can becompressed in a person's hand, like forming a snowball. However,immediately after forming it, a forceful impact (dropping or throwing)would return a hand compacted ball of the flowable solid to powder andother smaller pieces. In an embodiment, a flowable solid contains littleenough water that compressing the powder at several hundred psi does notsqueeze liquid water from the solid. In certain embodiments, the presentflowable solid can be a powder or a wetted powder.

Solid compositions can be made by merely blending the biocidal triaminewith the diacids in preferred ratios to obtain solid compositions.Pelletized materials can be manufactured by compressing the solidgranular or agglomerated materials in appropriate pelletizing equipmentto result in appropriately sized pelletized materials. Solid block andcast solid block materials can be made by introducing into a containereither a prehardened block of material or a castable liquid that hardensinto a solid block within a container. Preferred containers includedisposable plastic containers or water soluble film containers. Othersuitable packaging for the composition includes flexible bags, packets,shrink wrap, and water soluble film such as polyvinyl alcohol.

The solid compositions may be formed using a batch or continuous mixingsystem. In an exemplary embodiment, a single- or twin-screw extruder isused to combine and mix one or more components at high shear to form ahomogeneous mixture. In some embodiments, the processing temperature isat or below the melting temperature of the components. The processedmixture may be dispensed from the mixer by forming, casting or othersuitable means, whereupon the detergent composition hardens to a solidform. The structure of the matrix may be characterized according to itshardness, melting point, material distribution, crystal structure, andother like properties according to known methods in the art. Generally,a solid composition processed according to the method of the inventionis substantially homogeneous with regard to the distribution ofingredients throughout its mass and is dimensionally stable.

In an extrusion process, liquid and solid components are introduced intofinal mixing system and are continuously mixed until the components forma substantially homogeneous semi-solid mixture in which the componentsare distributed throughout its mass. The mixture is then discharged fromthe mixing system into, or through, a die or other shaping means. Theproduct is then packaged. In an exemplary embodiment, the formedcomposition begins to harden to a solid form in between approximately 1minute and approximately 3 hours. Particularly, the formed compositionbegins to harden to a solid form in between approximately 1 minute andapproximately 2 hours. More particularly, the formed composition beginsto harden to a solid form in between approximately 1 minute andapproximately 20 minutes.

In a casting process, liquid and solid components are introduced intothe final mixing system and are continuously mixed until the componentsform a substantially homogeneous liquid mixture in which the componentsare distributed throughout its mass. In an exemplary embodiment, thecomponents are mixed in the mixing system for at least approximately 60seconds. Once the mixing is complete, the product is transferred to apackaging container where solidification takes place. In an exemplaryembodiment, the cast composition begins to harden to a solid form inbetween approximately 1 minute and approximately 3 hours. Particularly,the cast composition begins to harden to a solid form in betweenapproximately 1 minute and approximately 2 hours. More particularly, thecast composition begins to harden to a solid form in betweenapproximately 1 minute and approximately 20 minutes.

In a pressed solid process, components are combined under pressure. In apressed solid process, flowable solids of the compositions are placedinto a form (e.g., a mold or container). The method can include gentlypressing the flowable solid in the form to produce the solidcomposition. Pressure may be applied by a block machine or a turntablepress, or the like. Pressure may be applied at ranges from about 1 toabout 3000 psi, or about 1 to about 1000 psi depending upon the blockshape and cylinder pressure. In certain embodiments, the methods canemploy pressures as low as greater than or equal to about 1 psi, greaterthan or equal to about 2, greater than or equal to about 5 psi, orgreater than or equal to about 10 psi. As used herein, the term “psi” or“pounds per square inch” refers to the actual pressure applied to theflowable solid being pressed and does not refer to the gauge orhydraulic pressure measured at a point in the apparatus doing thepressing. The method can include a curing step to produce the solidcomposition. As referred to herein, an uncured composition including theflowable solid is compressed to provide sufficient surface contactbetween particles making up the flowable solid that the uncuredcomposition will solidify into a stable solid composition. A sufficientquantity of particles (e.g. granules) in contact with one anotherprovides binding of particles to one another effective for making astable solid composition. Inclusion of a curing step may includeallowing the pressed solid to solidify for a period of time, such as afew hours, or about 1 day (or longer). In additional aspects, themethods could include vibrating the flowable solid in the form or mold,such as the methods disclosed in U.S. Pat. No. 8,889,048, which isherein incorporated by reference in its entirety.

The use of pressed solids provide numerous benefits over conventionalsolid block or tablet compositions requiring high pressure in a tabletpress, or casting requiring the melting of a composition consumingsignificant amounts of energy, and/or by extrusion requiring expensiveequipment and advanced technical know-how. Pressed solids overcome suchvarious limitations of other solid formulations for which there is aneed for making solid cleaning compositions. Moreover, pressed solidcompositions retain its shape under conditions in which the compositionmay be stored or handled.

By the term “solid”, it is meant that the hardened composition will notflow and will substantially retain its shape under moderate stress orpressure or mere gravity. A solid may be in various forms such as apowder, a flake, a granule, a pellet, a tablet, a lozenge, a puck, abriquette, a brick, a solid block, a unit dose, or another solid formknown to those of skill in the art. The degree of hardness of the solidcast composition and/or a pressed solid composition may range from thatof a fused solid product which is relatively dense and hard, forexample, like concrete, to a consistency characterized as being ahardened paste. In addition, the term “solid” refers to the state of thecomposition under the expected conditions of storage and use of thesolid detergent composition. In general, it is expected that thedetergent composition will remain in solid form when exposed totemperatures of up to approximately 100° F. and particularly up toapproximately 120° F.

The resulting solid composition may take forms including, but notlimited to: a cast solid product; an extruded, molded or formed solidpellet, block, tablet, powder, granule, flake; pressed solid; or theformed solid can thereafter be ground or formed into a powder, granule,or flake. In an exemplary embodiment, extruded pellet materials formedby the solidification matrix have a weight of between approximately 50grams and approximately 250 grams, extruded solids formed by thecomposition have a weight of approximately 100 grams or greater, andsolid block detergents formed by the composition have a mass of betweenapproximately 1 and approximately 10 kilograms. The solid compositionsprovide for a stabilized source of functional materials. In someembodiments, the solid composition may be dissolved, for example, in anaqueous or other medium, to create a concentrated and/or use solution.The solution may be directed to a storage reservoir for later use and/ordilution, or may be applied directly to a point of use.

The following patents disclose various combinations of solidification,binding and/or hardening agents that can be utilized in the solidcleaning compositions of the present invention. The following U.S.patents are incorporated herein by reference: U.S. Pat. Nos. 7,153,820;7,094,746; 7,087,569; 7,037,886; 6,831,054; 6,730,653; 6,660,707;6,653,266; 6,583,094; 6,410,495; 6,258,765; 6,177,392; 6,156,715;5,858,299; 5,316,688; 5,234,615; 5,198,198; 5,078,301; 4,595,520;4,680,134; RE32,763; and RE32818.

Methods of Use

The solid triamine compositions may be incorporated into a variety ofcleaning compositions, including for example floor cleaning composition,hard surface composition, or clean-in-place composition (i.e., forcleaning food and beverage or pharmaceutical equipment), detergentcompositions and the like. The system is especially useful in thefoodservice business on food soils. When a lipase is included in thesystem, the system and compositions are useful in removing fats and oilsoff of hard and soft surfaces in a kitchen. Fats and oils in a kitchenbuild up over time, eventually forming a hard coating on surfaces. Floortiles and back splashes near cooking surfaces eventually develop a sheento them because of the hardened layers of fat and oil. Grout becomesdiscolored as fat and oil soils become embedded into the grout. Bar ragsand mop heads accumulate fat and oil soils over time. In addition tohaving soil buildup, the foodservice industry needs to prevent outbreaksof food illness like E. coli and Salmonella. The invention is especiallyuseful in this industry because of its ability to remove food soils andits antimicrobial properties.

Exemplary floor cleaning compositions include compositions for use inmanual (i.e., mop and bucket) applications or in an automatic floorcleaning machines such as those manufactures by Tennant, Clarke andothers. When used in an automatic floor cleaning machine, thecomposition provides the additional benefit of maintaining thecleanliness of the inside of the machine through the action of theenzyme and preventing odor and bacterial growth in the machine becauseof the antimicrobial properties.

Foodservice industries often collect bar rags, towels, and mop heads ina bucket that includes a laundry pre-treatment composition. Thecompositions may be used as a pre-treatment composition in thefoodservice industry. The compositions are advantageous here becausethey can begin to break down food soils before the laundry even goesinto the laundry machine.

The solid composition of the present invention comprises the activeingredients in a high concentration. The concentration of the activeingredients is calculated on the total weight of the solid compositionof the present invention, if not otherwise stated. Before use, the solidcomposition of the present invention needs to be dissolved in an aqueoussolution, preferably water, to obtain a ready-to-use solution.Preferably, the solid composition can be dissolved at the time ofapplication and/or stored in a dilution device.

In some aspects the solid triamine compositions for use in generating aready-to-use solution may have a ratio of the diacid to the biocidaltriamine from about 1:10 to about 1:5, preferably from about 1:5 toabout 1:4, and most preferably from about 1:2 to about 1:3. In addition,without being limited according to the invention, all ranges for theratios recited are inclusive of the numbers defining the range.

Accordingly use of the solid triamine compositions may includeconcentrate compositions or may be diluted to form use compositions. Ingeneral, a concentrate refers to a composition that is intended to bediluted with water to provide a use solution that contacts an object toprovide the desired cleaning, rinsing, or the like. The triaminecomposition that contacts the articles or surfaces to be washed,sanitized, disinfected or the like can be referred to as a concentrateor a use composition (or use solution) dependent upon the formulationemployed in methods according to the invention. It should be understoodthat the concentration of the biocidal triamine, diacid and additionalfunctional ingredients in the composition will vary depending on whetherthe composition is employed as a concentrate or as a use solution.

A use solution may be prepared from the concentrate by diluting theconcentrate with water at a dilution ratio that provides a use solutionhaving desired detersive properties. The water that is used to dilutethe concentrate to form the use composition can be referred to as waterof dilution or a diluent, and can vary from one location to another. Thetypical dilution factor is between approximately 1 and approximately10,000 but will depend on factors including water hardness, the amountof soil to be removed and the like. In an embodiment, the concentrate isdiluted at a ratio of between about 1:10 and about 1:10,000 concentrateto water. Particularly, the concentrate is diluted at a ratio of betweenabout 1:100 and about 1:5,000 concentrate to water. More particularly,the concentrate is diluted at a ratio of between about 1:250 and about1:2,000 concentrate to water, and preferably between about 1:500 andabout 1:750.

In an aspect of the invention, a use solution of the biocidal triaminecomposition provides between about 1 ppm to about 1000 ppm triamine, andbetween about 1 ppm to about 500 ppm diacid. In a preferred aspect ofthe invention, a use solution of the biocidal triamine composition hasbetween about 1 ppm to about 500 ppm triamine, and between about 1 ppmto about 250 ppm diacid. In addition, without being limited according tothe invention, all ranges recited are inclusive of the numbers definingthe range and include each integer within the defined range.

According to the invention, the solid composition can be dissolved inservice water, deionized water or such at a sufficient proportion toobtain the concentrated solution and/or diluted ready-to-use solutionset forth above.

All publications and patent applications in this specification areindicative of the level of ordinary skill in the art to which thisinvention pertains. All publications and patent applications are hereinincorporated by reference to the same extent as if each individualpublication or patent application was specifically and individuallyindicated as incorporated by reference.

EXAMPLES

Embodiments of the present invention are further defined in thefollowing non-limiting Examples. It should be understood that theseExamples, while indicating certain embodiments of the invention, aregiven by way of illustration only. From the above discussion and theseExamples, one skilled in the art can ascertain the essentialcharacteristics of this invention, and without departing from the spiritand scope thereof, can make various changes and modifications of theembodiments of the invention to adapt it to various usages andconditions. Thus, various modifications of the embodiments of theinvention, in addition to those shown and described herein, will beapparent to those skilled in the art from the foregoing description.Such modifications are also intended to fall within the scope of theappended claims.

Example 1

Methods for producing pressed solid compositions for commercialsanitizing compositions employing biocidal triamines and enzymes wereevaluated. Desired solidified compositions required performance efficacythat meets or preferably exceeds the commercially-available liquidproduct performance, as measured by cleaning performance and microefficacy (i.e. sanitizing capability), along with other measurableincluding for example, odor reduction. Exemplary formulations evaluatedfor replacement solid compositions are set forth in Table 4.

TABLE 4 Liquid Sanitizing Liquid Composition Composition Description(wt-%) (wt-%) Water DI 70-85 50-65 Triamine (Lonzabac 12.100) 2-4  0Acidulants  5-10  5-10 Lipase enzyme 1-5 1-5 Additional FunctionalIngredients 15-45 35-50 Total 100 100

For the evalulated formulations the additional functional ingredientsincluded Alcohol Linear C12-16 ethoxylate, Polyether Siloxanes 5843 DRM,Amine oxide surfactant, and Monoethanolamine 99% IBC included in bothcompositions.

Solidification evaluations first evaluated neutralization of thebiocidal triamine from an alkaline pH in the liquid formulation prior tosolidification due to the liquid formulations requiring neutralizationof the biocidal triamine from the alkaline pH of about 10-11 to a pH ofabout 8.5 for stabilization of the lipase enzyme formulated therein. Theneutralization of the biocidal triamine minimizes enzyme degradationwithin the composition, while maximizing enzyme stability. The biocidaltriamine Lonzabac 12.100 available from Lonza Inc. was evaluated forsolid compositions as the triamine is commercially-available in liquidformulations as shown in Table 2.

As shown in Table 5, various acids were combined in varyingconcentrations with the biocidal triamine Lonzabac 12.100 to assess thestabilization of the neutralized compositions for use in a solidcomposition. The desired amounts of triamine were weighed out andcombined with the desired amounts of the evaluated solid acids. Thetriamine and acids were gently mixed to disperse the acid in thetriamine. The solutions were left undisturbed for approximately 1.5-2.5hours and observations on the form of the triamine/acid mixture weremade. If the mixture had expanded into a powder it was gently mixed toseparate particles. For each evaluation a 1% solution of each powder wasmade to determine solubility and pH.

TABLE 5 % Acid % amine acid:amine Water pH ID Acid Amine MW (wt-%)(wt-%) (molar) Observations solubility of 1% 1 Citric Lonzabac 192 25 750.519097222 Free flow- Cloudy/ppt/ N/A 12.100 ing powder gel ball 2Tartaric Lonzabac 150 18.2 81.2 0.446781609 Free flow- Clear 9.26 12.100ing powder solution 3 Tartaric Lonzabac 150 25 75 0.664444444 Free flow-Clear 8.85 12.100 ing powder solution 4 Tartaric Lonzabac 150 30.7 69.30.883049543 Free flow- Clear 8.29 12.100 ing powder solution 5 TartaricLonzabac 150 35.7 64.3 1.106718507 Free flow- Clear 7.48 12.100 ingpowder solution 6 Benzoic Lonzabac 122 25 75 0.816939891 Waxy solidClear 8.76 12.100 solution 7 Mandelic Lonzabac 152 25 75 0.655701754Very Cloudy 8.05 12.100 hard solid white soln 8 Sulfamic Lonzabac 97 2575 1.027491409 very Clear 8.33 12.100 hard solid solution 9 BoricLonzabac 62 25 75 1.607526882 Clear gel base Clear 8.18 12.100 w/pwdrtop solution 10 Malic Lonzabac 134 25 75 0.743781095 Free flow- Clear7.87 12.100 ing powder solution 11 Malonic Lonzabac 104 25 750.958333333 Hard solid Clear 7.38 12.100 solution 12 Maleic Lonzabac 11625 75 0.859195402 hard solid, Clear 7.89 12.100 broke into pwdr solution13 Succinic Lonzabac 118 25 75 0.844632768 Very Clear 8.04 12.100 hardsolid solution 14 Adipic Lonzabac 146 25 75 0.682648402 Very Clear 8.1612.100 hard solid solution 15 Aspartic Lonzabac 133 25 75 0.749373434Very thick 12.100 paste, grainy 16 EDTA Lonzabac 292 36 64 0.575984589damp powder Clear w/some 8.41 Acid 12.100 EDTA ppt 17 IDA Lonzabac 13325 75 0.749373434 dry powder, clear 8.95 12.100 did not swell 18 glycineLonzabac 75 25 75 1.328888889 wet powder Cloudy N/A 12.100 19 glycineLonzabac 75 50 50 3.986666667 dry powder Cloudy N/A 12.100 20 lysineLonzabac 146 25 75 0.682648402 dry powder Cloudy N/A 12.100 21 lysineLonzabac 146 50 50 2.047945205 dry powder Cloudy N/A 12.100 22 gluconicLonzabac 196 25 75 0.508503401 waxy solid Clear 8.94 12.100 23 gluconicLonzabac 196 50 50 1.525510204 hard Clear 8.41 12.100 waxy solid 24glutamic Lonzabac 147 25 75 0.678004535 dry powder Clear 8.48 12.100 25glutamic Lonzabac 147 50 50 2.034013605 hard Clear 8.1  12.100 brittlesolid 26 dipicolinic Lonzabac 167 25 75 0.596806387 dry powder Hazy 8.9412.100 27 dipicolinic Lonzabac 167 50 50 1.790419162 very ppt on 4.7112.100 hard solid bottom 28 octanoic Lonzabac 144 25 75 0.69212963opaque cream Clear 9.61 12.100 29 octanoic Lonzabac 144 50 502.076388889 orange Clear 7.59 12.100 waxy solid 30 decanoic Lonzabac 17225 75 0.579457364 opaque cream Cloudy/ppt/ N/A acid 12.100 gel ball 31decanoic Lonzabac 172 50 50 1.738372093 orange Clear 9.26 acid 12.100waxy solid solution

As set forth in Table 5, the step of neutralizing the alkaline biocidaltriamine with a solid acid unexpectedly resulted in a number of solidtriamine compositions. Free flowing powders, hard solids and very hardsolids were unexpectedly obtained from the reaction of the triamine withthe solid acids. The pastes generated were not sufficiently solidifiedto proceed for additional evaluation. In an aspect of the invention,combinations of triamines with a solid acid resulting in a compositionhaving a water content of 10 wt-% or greater of water are undesirableformulations. As a further unexpected benefit the solid biocidaltriamines allowed formulation containing predominately active triamine.In an aspect, at least about 90 wt-% active biocidal triamine can beformulated into the solid compositions.

Example 2

Following the testing of Example 1 looking at the neutralization of thebiocidal triamine with a solid acid, additional solid acids wereevaluated at the 25:75 ratio/% acid to triamine as shown in Table 6.

TABLE 6 Acid % Acid % Amine molar Water pH Acid MW MP (wt-%) (wt-%)ratio Solubility of 1% Observations Formic 46.03 47.1 25 75 2.16525454N/A N/A Gel ball formed; vigerous reaction; discoloration Acetic 60.0561 25 75 1.659728 Yes 8.31 Very hard solid formed Acrylic 72.06 57 25 751.38310667 No N/A Hard gel formed; not flowable but malleable Sorbic 112275 25 75 0.88988095 Yes 9.26 Waxy soft solid formed Fumaric 116.07 54825 75 0.85867724 Yes 8.65 Solidified into paste consistency maleic116.07 275 25 75 0.85867724 Yes 7.89 Hard solid formed; broke intopowder Caproic 116.16 25.9 25 75 0.85801194 Yes 9.21 Did not solidify;homogenous (hexanoic) liquid Succinic 118.09 363 25 75 0.84398905 Yes8.04 Very hard solid formed Benzoic 122 252 25 75 0.81693989 Yes 8.76Hard solid formed Oxalic 126.07 216 25 75 0.79056609 No N/A Very hardsolid formed; rapid (ethanedioic) solidification; discoloration Malic134 266 25 75 0.74378109 Yes 7.87 Free flowing powder formed Salicylic138 317 25 75 0.72222222 N/A N/A Did not react; powder on bottom, liquidon top Tartaric 150 170 25 75 0.66444444 Yes 9.26 Free flowing powderformed mandelic 152 246 25 75 0.65570175 No 8.05 Very hard solid formedCitric 192 313 25 75 0.51909722 No N/A Free flowing powder formedGluconic 196 268 25 75 0.5085034 Yes 8.41 Waxy solid formed

Example 3

Additional formulations of the biocidal triamine and solid acid werefurther evaluated to assess melting points and percent water content inthe formulated pressed solid compositions. Exemplary formulations areshown in Table 7 were formulated into pressed solids after following theexperimentation set forth in Example 1.

TABLE 7 Water Melting point Content Contents (wt-%) (° C.) (wt-%) 81.8%lonzabac + 18.2% Tartaric acid 57.57 0.6 75% lonzabac + 25% Tartaricacid 55.38 0.6 69.3% lonzabac + 30.7% Tartaric acid 75.5 0.5 64.3%lonzabac + 35.7% Tartaric acid 73.11 0.6 75% lonzabac + 25% Malic acid85.55 0.5 22.5% lonzabac + 7.5% Tartaric + 35% 51.15 4.2 4Na-EDTA + 35%Na Sulfate 64.3% Lonzabac + 35.7% Acid EDTA 113.95 0.7 75% Lonzabac +25% Aspartic acid 76.25 0.5 75% lonzabac + 25% Citric acid 87.91 0.6

The results shown in Table 7 reflect a preferred pressed solidcomposition having a water content of less than 1 wt-%.

Example 4

Various formulations of the biocidal triamine and solid acid werefurther evaluated for formulation into pressed solid compositions. Theexemplary formulations are shown in Table 8 were formulated into pressedsolids after following the experimentation set forth in Example 1.

TABLE 8 Tablet 1 Tablet 2 Tablet 3 Tablet 4 Description (wt-%) (wt-%)(wt-%) (wt-%) Lonzabac 12.100 75 64.3 22.5 22.5 Tartaric acid 25 35.77.5 7.5 Tetrasodium EDTA 0 0 35 35 Sodium Sulfate 0 0 35 0 anhydrousUrea 0 0 0 35 Total 100 100 100 100

50 grams of each of the tablet formulations were weighted to be pressed.Then a 50 gram sample was placed into a small 1.5″ diameter stainlesssteel dye and pressed using a carver press at 2000 psi for 20 seconds.The tablet was then removed from the dye. The results indicated that thepressed tablets were hard and retained their shape upon being ejectedfrom the mold.

The inventions being thus described, it will be obvious that the samemay be varied in many ways. Such variations are not to be regarded as adeparture from the spirit and scope of the inventions and all suchmodifications are intended to be included within the scope of thefollowing claims.

The above specification provides a description of the manufacture anduse of the disclosed compositions and methods. Since many embodimentscan be made without departing from the spirit and scope of theinvention, the invention resides in the claims.

What is claimed is:
 1. A method of making a solid triamine compositioncomprising: mixing a triamine and an acid, wherein the ratio of the acidto the triamine is from about 1:10 to about 1:1; and at least partiallyneutralizing the triamine to a pH of about 6 to about 11 to form a solidamine salt.
 2. The method of claim 1, wherein the acid is a monoacid ordiacid.
 3. The method of claim 1, wherein the acid is selected from thegroup consisting of citric, tartaric, malic, maleic, malonic, succinic,adipic, aspartic, glutamic, dipicolinic, and dodecanoic.
 4. The methodof claim 2, wherein the monoacid has the formula R—COOH wherein R is abranched or linear C4-C20 alkane or alkene, and wherein the diacid isselected from the group consisting of the structure of (a), (b), (c) andcombinations thereof, as shown:

wherein: n=1-20, R₁ is H, C1-C8 alkyl or COOH, R₂ is H, C1-C8 alkyl,NH₂, OH, or COOH, and R₁ and R₂ substitution occurs on at least onecarbon within C1-C20 chain;

wherein: R₁ and R₂ are each COOH; R₃, R₄, R₅ and R₆ independently are H,C1-C8 alkyl, OH, or NH₂, R₁ and R₃ are each COOH; R₂, R₄, R₅, and R₆independently are H, C1-C8 alkyl, OH, or NH₂, R₁ and R₄ are each COOH;R₂, R₃, R₅, and R₆ independently are H, C1-C8 alkyl, OH, or NH₂, R₁ andR₅ are each COOH; R₂, R₃, R₄, and R₆ independently are H, C1-C8 alkyl,OH, or NH₂, or R₁ and R₆ are each COOH; R₂, R₃, R₄, and R₅ independentlyare H, C1-C8 alkyl, OH, or NH₂;

wherein: R₁ and R₂ are COOH; R₃, R₄, and R₅ independently are H, C1-C8alkyl, OH, or NH₂; R₁ and R₃ are COOH; R₂, R₄, R₅ independently are H,C1-C8 alkyl, OH, or NH₂; R₁ and R₄ are COOH; R₂, R₃, R₅ independentlyare H, C1-C8 alkyl, OH, or NH₂; or R₁ and R₅ are COOH; R₂, R₃, R₄independently are H, C1-C8 alkyl, OH, or NH₂.
 5. The method of claim 1,wherein the triamine has the following formula:

wherein R is a straight chain C1-C12 alkyl group.
 6. The method of claim1, wherein the triame has any one of the following formulas:R—NH—(CH₂)_(r)NH₂   (1a)R—NH—(CH₂)_(r)N⁺H₃X″  (1b)R—N⁺H₂—(CH₂)_(r)NH₃2X⁻  (1c)R—NH——[(CH₂)_(r)NH]_(y)—(CH₂)_(m)—NH₂   (2a)R—NH—[(CH₂)_(r)—NH]_(y)(CH₂)_(m)—NH₂(H⁺X⁻)_(n)   (2b)R₂—NY   (3a)R₂—NY2⁺X″  (3b), wherein: R is a linear or branched alkyl residue with 6to 22C atoms, Y independently represents hydrogen or a methyl group, X″is an equivalent of an anion comprising an amidosulfonate, nitrate,halide, sulfate, hydrogen carbonate, carbonate, phosphate, hydroxide,carboxylate, and/or organic acid, m, r, and y independently represent aninteger ranging from 1 to 6, and n is an integer ranging from 1 to 2+y.7. The method of claim 1, wherein the concentration of the triamine isbetween about 10 and about 99 wt-% and the concentration of the acid isbetween about 1 and about 50 wt-%, and wherein the solid triaminesremains solid at temperatures up to about 50° C.
 8. The method of claim1, wherein the solid is a powder, paste or hardened solid and whereinthe solid has a water content of less than about 10 wt-%.
 9. The methodof claim 1, wherein the step of at least partially neutralizing thetriamine neutralizes the pH to about 6.5 to about 9.5.
 10. The method ofclaim 1, wherein the step of at least partially neutralizing thetriamine neutralizes the pH to about 7 to about
 9. 11. The method ofclaim 1, wherein the step of at least partially neutralizing thetriamine occurs prior to solidification to stabilize the solid triamine.12. The method of claim 1, wherein the mixing occurs in a mixing vesselto provide a substantially homogenous mixture.
 13. The method of claim1, wherein the mixing occurs in a continuous or batch process, andwherein the formation of the solid triamines occurs over a period fromabout 15 minutes to about 48 hours.
 14. The method of claim 1, whereinthe reaction occurs at a temperature between about 70° F. (21° C.) andabout 130° F. (55° C.).
 15. The method of claim 1, wherein the ratio ofthe diacid to the biocidal triamine is from about 1:5 to about 1:1. 16.The method of claim 1, wherein the solidification does not require amelt and/or conventional casting and/or extruding to compress the solidtriamine through a die.
 17. The method of claim 1, wherein no water isadded to the reaction and/or a chelant is added to reduce the watercontent of the solid composition.
 18. A method of cleaning, sanitizingand/or disinfecting comprising: generating a solid triamine according toclaim 1; and optionally adding additional functional ingredients to thesolid triamine and/or forming a composition comprising the solidtriamine and additional functional ingredients, and contacting anarticle or surface with a use solution of the solid triamine and/or ause solution of the composition for cleaning, sanitizing, and/ordisinfecting.
 19. The method of claim 18, wherein the cleaning,sanitizing, and/or disinfecting is a rinse step and/or lubricating step.20. The method of claim 18, wherein the use solution of the solidtriamine and/or compositions comprising the solid triamines providesbetween about 1 ppm to about 1000 ppm triamine, and between about 1 ppmto about 500 ppm acid.